Footwear sole structure having a composite element and methods for manufacturing same

ABSTRACT

One or more aspects of the present disclosure provide for composite elements that include a textile having a plurality of fibers, the plurality of fibers comprising a first thermoplastic material; and a second thermoplastic material surrounding the plurality of fibers of the textile and consolidating at least a portion of the textile, wherein the second thermoplastic material has a melting temperature lower than a melting temperature of the first thermoplastic material. The composite elements can be used as part of a cushioning structure, whereby the composite element imparts puncture resistant to the cushioning structure. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/747,967, filed on Oct. 19, 2018, and 62/748,005, filed on Oct. 19,2018, each of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure relates to articles, such as articles of apparel,articles of footwear, and articles of sporting equipment. Morespecifically, the present disclosure is directed to articles comprisinga composite element comprising a textile having a plurality of fibersincluding a first thermoplastic material and a second thermoplasticmaterial surrounding the plurality of fibers of the textile, and tomethods of making the disclosed articles.

BACKGROUND

The design of athletic equipment and apparel as well as footwearinvolves a variety of factors from the aesthetic aspects, to the comfortand feel, to the performance and durability. While design and fashionmay be rapidly changing, the demand for increasing performance in themarket is unchanging. To balance these demands, designers employ avariety of materials and designs for the various components that make upathletic equipment and apparel as well as footwear.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciatedupon review of the detailed description, described below, when taken inconjunction with the accompanying drawings.

FIG. 1 is an elevation view of an article of footwear with a solecomponent according to an aspect of the invention.

FIG. 2 is an exploded view of the sole component of the article offootwear of FIG. 1.

FIG. 3 is a plan view of the bottom of the sole component of the articleof footwear of FIG.

FIG. 4 is a bottom view of an insert for use in a sole component of anarticle of footwear.

FIG. 5 is a top view of the insert of FIG. 4 inserted in a first portionto form a sole component.

FIGS. 6A-6D are cross-sectional plan views of disclosed compositeelements. Each of FIGS. 6A and 6B show a cross-sectional plan view of adisclosed composite element comprising a non-woven textile having aplurality of fibers in which the plurality of fibers comprise a firstthermoplastic material, and in which a second thermoplastic materialsurrounds the plurality of fibers and consolidates the textile. FIG. 6Cis a cross-sectional plan view of a disclosed composite elementcomprising a textile having a plurality of filaments or yarns in whichthe plurality of filaments or yarns comprise a first thermoplasticmaterial, and in which a second thermoplastic material surrounds theplurality of fibers and consolidates the textile. FIG. 6D is across-sectional plan view of a disclosed composite element comprisingtwo textiles such that each textile has a plurality of filaments oryarns in which the plurality of filaments or yarns comprise a firstthermoplastic material, and in which a second thermoplastic materialsurrounds the plurality of fibers and consolidates the textiles. FIG. 6Eis a cross-sectional plan view of a disclosed composite elementcomprising a plurality of textiles such that each textile has aplurality of filaments or yarns in which the plurality of filaments oryarns comprise a first thermoplastic material, and in which a secondthermoplastic material surrounds the plurality of fibers andconsolidates the textiles.

FIG. 7 is a cross-sectional plan view of a disclosed composite elementcomprising a textile component having a plurality of fibers in which theplurality of fibers comprise a first thermoplastic material, and inwhich a second thermoplastic material surrounds the plurality of fibersand consolidates the textile. The textile has a first face and a secondface, with yarns connecting the first face and the second face.

FIGS. 8A-8B are cross-sectional plan views of disclosed cushioningstructures comprising a first cushioning element that is a fluid chamberand a disclosed composite element. FIG. 8A shows a cushioning structurecomprising a cushioning element that is a fluid chamber and a disclosedcomposite element that is in contact with an interior face of the firstcushioning element.

FIG. 8B shows a cushioning structure comprising a cushioning elementthat is a fluid chamber and a disclosed composite element that is incontact with an exterior face of the first cushioning element.

FIGS. 9A-9B are cross-sectional plan views of disclosed cushioningstructures comprising a one or more cushioning elements that are foamcomponents and a disclosed composite element. FIG. 9A shows a cushioningstructure comprising a first cushioning element and a second cushioningelement, each of which is a foam component, and a disclosed compositeelement that is affixed with a face of the first cushioning element andthe second cushioning element. FIG. 9B shows a cushioning structurecomprising a first cushioning element that is a foam component and adisclosed composite element that is affixed to an exterior face of thefirst cushioning element.

DETAILED DESCRIPTION

The present disclosure provides for composite elements comprising: atextile including a plurality of fibers, the plurality of fiberscomprising a first thermoplastic material; and a second thermoplasticmaterial surrounding the plurality of fibers of the textile andconsolidating at least a portion of the textile, wherein the secondthermoplastic material has a melting temperature lower than a meltingtemperature of the first thermoplastic material. The composite elementcan be used alone or as an element in a component, article or structure.For example, the composite element can be used as part of a fluidchamber or a cushioning structure. A component, article or structurecomprising the composite element has improved puncture resistancecompared to the component, article or structure lacking the compositeelement.

According to various aspects, a composite element can be used as part ofa fluid chamber. For example, a fluid chamber can comprise a compositeelement extending across and affixed to at least a portion of the firstside of the fluid chamber, to the second side of the fluid chamber, tothe sidewall of the fluid chamber, or to any combination thereof;wherein the composite element comprises a textile including a pluralityof fibers, the plurality of fibers comprising a first thermoplasticmaterial, and a second thermoplastic material surrounding and theplurality of fibers in the textile and consolidating the textile, thesecond thermoplastic material having a melting temperature lower than amelting temperature of the first thermoplastic material; and a fluidchamber having a first side, a second side, and a sidewall extendingbetween the first side and the second side, the fluid chamber comprisinga third thermoplastic material.

In an aspect, a composite element can be used as part of a cushioningstructure. For example, a cushioning structure can comprise a firstcushioning element; and a composite element affixed to the cushioningelement, wherein the composite element comprises a textile including aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and a second thermoplastic material, wherein thesecond thermoplastic material has a melting temperature lower than amelting temperature of the first thermoplastic material; wherein, in thecomposite element, the second thermoplastic material surrounds theplurality of fibers in the textile and consolidates the textile.

The present disclosure relates to articles of footwear, comprising anupper; and a sole structure affixed to the upper, wherein the solestructure includes a disclosed cushioning structure comprising adisclosed composite element.

The present disclosure also relates to outsoles for an articles offootwear, the outsole comprising a disclosed composite element.

In various aspects, the present disclosure provides for a method ofmanufacturing a composite element, the method comprising: positioning atextile and film adjacent to each other, wherein the textile includes aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and wherein the film comprises a secondthermoplastic material has a melting temperature lower than a meltingtemperature of the first thermoplastic material; and increasing atemperature of the film to a temperature at or above the meltingtemperature of the second thermoplastic material but below the meltingtemperature of the first thermoplastic material, such that the secondthermoplastic flows and surrounds the plurality of fibers of the textileand consolidates the textile; and decreasing the temperature of the filmto a temperature below the melting temperature of the secondthermoplastic material such that the second thermoplastic re-solidifies,forming the composite element.

The present disclosure provides for a method of forming a fluid chamber,the method comprising: affixing a composite element to a fluid chamber,wherein the fluid chamber has a first side, a second side, and asidewall extending between the first side and the second side, and thefluid chamber comprises a third thermoplastic material; wherein thecomposite element extends across and affixed to at least a portion ofthe first side of the fluid chamber, to the second side of the fluidchamber, to the sidewall of the fluid chamber, or to any combinationthereof, and wherein the composite element comprises a textile includinga plurality of fibers, the plurality of fibers comprising a firstthermoplastic material, and a second thermoplastic material surroundingand the plurality of fibers in the textile and consolidating thetextile, the second thermoplastic material having a melting temperaturelower than a melting temperature of the first thermoplastic material.

The present disclosure provides for a method of making a cushioningstructure, the method comprising: affixing a composite element to afirst cushioning element; wherein the composite element comprises atextile including a plurality of fibers, the plurality of fiberscomprising a first thermoplastic material; a second thermoplasticmaterial, wherein the second thermoplastic material has a meltingtemperature lower than a melting temperature of the first thermoplasticmaterial; and, in the composite element, the second thermoplasticmaterial surrounds the plurality of fibers in the textile andconsolidates the textile.

The present disclosure provides for a method of manufacturing anarticle, comprising: affixing a first component to a cushioningstructure, wherein the cushioning structure is a disclosed cushioningstructure.

In a first aspect, the present disclosure is directed to a compositeelement comprising: a textile including a plurality of fibers, theplurality of fibers comprising a first thermoplastic material; and asecond thermoplastic material surrounding the plurality of fibers of thetextile and consolidating at least a portion of the textile, wherein thesecond thermoplastic material has a melting temperature lower than amelting temperature of the first thermoplastic material.

In a second aspect, the present disclosure is directed to a cushioningstructure comprising: a first cushioning element; and a compositeelement affixed to the first cushioning element, wherein the compositeelement comprises a textile including a plurality of fibers, theplurality of fibers comprising a first thermoplastic material; and asecond thermoplastic material, wherein the second thermoplastic materialhas a melting temperature lower than a melting temperature of the firstthermoplastic material; wherein, in the composite element, the secondthermoplastic material surrounds the plurality of fibers in the textileand consolidates the textile.

In a third aspect, the present disclosure is directed to an article offootwear, comprising: an upper; and a sole structure affixed to theupper, wherein the sole structure includes a cushioning structureaccording to any one of disclosed cushioning structure, e.g., accordingthe foregoing second aspect and related cushioning structures asdisclosed herein.

In a fourth aspect, the present disclosure is directed to an outsole foran article of footwear, the outsole comprising: a composite elementaccording to any one of disclosed composite element, e.g., according theforegoing first aspect and related composite elements as disclosedherein.

In a fifth aspect, the present disclosure is directed to a method ofmanufacturing a composite element, the method comprising: positioning atextile and film adjacent to each other, wherein the textile includes aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and wherein the film comprises a secondthermoplastic material has a melting temperature lower than a meltingtemperature of the first thermoplastic material; and increasing atemperature of the film to a temperature at or above the meltingtemperature of the second thermoplastic material but below the meltingtemperature of the first thermoplastic material, such that the secondthermoplastic flows and surrounds the plurality of fibers of the textileand consolidates the textile; and decreasing the temperature of the filmto a temperature below the melting temperature of the secondthermoplastic material such that the second thermoplastic re-solidifies,forming the composite element.

In a sixth aspect, the present disclosure is directed to a method ofmaking a cushioning structure, the method comprising: affixing acomposite element to a first cushioning element; wherein the compositeelement comprises a textile including a plurality of fibers, theplurality of fibers comprising a first thermoplastic material; a secondthermoplastic material, wherein the second thermoplastic material has amelting temperature lower than a melting temperature of the firstthermoplastic material; and, in the composite element, the secondthermoplastic material surrounds the plurality of fibers in the textileand consolidates the textile.

In a seventh aspect, the present disclosure is directed to a method ofmanufacturing an article, comprising: affixing a first component to acushioning structure, wherein the cushioning structure is a cushioningstructure according to any one of disclosed cushioning structure, e.g.,according the foregoing second aspect and related cushioning structuresas disclosed herein.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

Exemplary Articles Comprising a Composite Element

Articles of the present disclosure include the composite element, whichis understood to comprise the composite element itself or a componentsuch as a fluid chamber or a cushioning structure comprising thecomposite element. In an aspect, a disclosed article including acomposite element can include footwear, apparel (e.g., shirts, jerseys,pants, shorts, gloves, glasses, socks, hats, caps, jackets,undergarments), containers (e.g., backpacks, bags), and upholstery forfurniture (e.g., chairs, couches, car seats), bed coverings (e.g.,sheets, blankets), table coverings, towels, flags, tents, sails, andparachutes. In addition, the composite element can be used with itemssuch as striking devices (e.g., bats, rackets, sticks, mallets, golfclubs, paddles, etc.), athletic equipment (e.g., golf bags, baseball andfootball gloves, soccer ball restriction structures), protectiveequipment (e.g., pads, helmets, guards, visors, masks, goggles, etc.),locomotive equipment (e.g., bicycles, motorcycles, skateboards, cars,trucks, boats, surfboards, skis, snowboards, etc.), balls or pucks foruse in various sports, fishing or hunting equipment, furniture,electronic equipment, construction materials, eyewear, timepieces,jewelry, and the like.

In certain aspects, a disclosed composite element can form at least aportion of a component of an article of footwear. In certain aspects,the disclosed composite elements can form at least a portion of acomponent of an article of sporting equipment. For example, thedisclosed composite elements can comprise a portion of an outsole for ashoe, such as an athletic shoe.

In an aspect, the article can include footwear. The footwear can bedesigned for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, and the like, whether as anathletic performance surface or as a general outdoor surface. However,the article of footwear may also be desirable for indoor applications,such as indoor sports including dirt playing surfaces for example (e.g.,indoor baseball fields with dirt infields).

The article of footwear can be designed for use in outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like. The article of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, andspikes as well as tread patterns) to provide traction on soft andslippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

The article can be an article of apparel (i.e., a garment). The articleof apparel can be an article of apparel designed for athletic or leisureactivities. The article of apparel can be an article of apparel designedto provide protection from the elements (e.g., wind and/or rain), orfrom impacts.

The article can be an article of sporting equipment. The article ofsporting equipment can be designed for use in indoor or outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like.

Exemplary Aspects of Articles of Footwear

Footwear 10 is an exemplary article of athletic footwear that comprisesone or more components article made using the methods of the presentdisclosure. While illustrated as a running shoe, footwear 10 mayalternatively be configured for any suitable athletic performance, suchas baseball shoes, basketball shoes, soccer/global football shoes,American football shoes, running shoes, cross-trainer shoes,cheerleading shoes, golf shoes, and the like. While an athletic shoe isexemplified in FIG. 1, it will be readily understood that some of theterminology employed will also apply to other articles of footwear or toother styles of shoe. Footwear 10 includes an upper 12 and a solecomponent 14 secured to upper 12. Sole component 14 can be secured toupper 12 by adhesive or any other suitable means. As used herein, thesole component 14 can be a monolithic component formed entirely of anarticle made using the disclosed methods as described herein, or amulti-component assembly formed of a plurality of monolithic components,where at least one of the monolithic components is formed entirely ofthe article made using the disclosed methods as described herein.

Footwear 10 has a medial, or inner, side 16 and a lateral, or outer,side 18. For ease of discussion, footwear 10 can be divided into threeportions: a forefoot portion 20, a midfoot portion 22, and a heelportion 24. Portions 20, 22, and 24 are not intended to demarcateprecise areas of footwear 10. Rather, portions 20, 22, and 24 areintended to represent respective areas of footwear 10 that provide aframe of reference during the following discussion. Unless indicatedotherwise, directional terms used herein, such as rearwardly, forwardly,top, bottom, inwardly, downwardly, upwardly, etc., refer to directionsrelative to footwear 10 itself. Footwear 10 is shown in FIG. 1 in asubstantially horizontal orientation, as it would be positioned on ahorizontal surface when worn by a wearer. However, it is to beappreciated that footwear 10 need not be limited to such an orientation.Thus, in FIG. 1, rearwardly is toward heel portion 24 (to the right asseen in FIG. 1), forwardly is toward forefoot portion 20 (to the left asseen in FIG. 1), and downwardly is toward the bottom of the page as seenin FIG. 1. Top refers to elements toward the top of the view in FIG. 1,while bottom refers to elements toward the bottom of the view in FIG. 1.Inwardly is toward the center of footwear 10, and outwardly is towardthe outer peripheral edge of footwear 10.

In some aspects, the component is a sole component, such as a solecomponent 14 depicted in FIGS. 1-5, that includes article made using thedisclosed methods as described herein. In some aspects, the component isan insert such as insert 36 or insert 60 depicted in FIGS. 4-5 thatincludes article made using the disclosed methods as described herein.The sole components and inserts for sole components can be madepartially or entirely of article made using the disclosed methods asdescribed herein. Any portion of a sole component or an insert for asole component can be made of article made using the disclosed methodsas described herein. For example, first portion 26 of the sole component(optionally including the ground engaging lower surface 44, such as theplurality of projections 46 and/or the groove 48 surrounding theprojections), the entire insert 36, portions 62 or 64 of insert 60, aseparate outsole component, or any combination thereof, can includearticle made using the disclosed methods as described herein.

Sole component 14, which is generally disposed between the foot of thewearer and the ground, provides attenuation of ground reaction forces(i.e., imparting cushioning), traction, and may control foot motions,such as pronation. As with conventional articles of footwear, solecomponent 14 can include an insole (not shown) located within upper 12.In some aspects, the sole component is an insole or sockliner or is amulti-component assembly including an insole or sockliner, can furtherinclude an insole or sockliner located within the upper, where theinsole or sockliner is formed entirely or partially of article madeusing the disclosed methods as described herein. Articles of footweardescribed herein can include an insole or sockliner formed entirely orpartially of article made using the disclosed methods as describedherein.

As can be seen in FIG. 2, sole component 14 consists of a first portion26 having an upper surface 27 with a recess 28 formed therein. Uppersurface 27 is secured to upper 12 with adhesive or other suitablefastening means. A plurality of substantially horizontal ribs 30 isformed on the exterior of first portion 26. In certain aspects, ribs 30extend from a central portion of forefoot portion 20 on medial side 16rearwardly along first portion 26, around heel portion 24 and forwardlyon lateral side 18 of first portion 26 to a central portion of forefootportion 20.

First portion 26 provides the external traction surface of solecomponent 14. In certain aspects it is to be appreciated that a separateoutsole component could be secured to the lower surface of first portion26. When a separate outsole component is secured to the lower surface offirst portion 26, the first portion 26 is a midsole component. In someaspects, the article is a midsole component for an article of footwear.

In some aspects, the article is an insert. An insert 36 can be receivedin recess 28. As illustrated in FIG. 2, insert 36 can provide cushioningor resiliency in the sole component. First portion 26 can providestructure and support for insert 36. In such aspects, first portion 26can be formed of a material of higher density and/or hardness ascompared to insert 36 such as, for example, non-foam materials includingrubber and thermoplastic polyurethane, as well as foam materials. Incertain aspects, insert 36 can be formed of article made using thedisclosed methods as described herein.

Insert 36 has a curved rear surface 38 to mate with curved rear surface32 of recess 28 and a transverse front surface 40 to mate withtransverse front surface 34 of recess 28. An upper surface 42 of insert36 is in contact with and secured to upper 12 with adhesive or othersuitable fastening means. For example, when there is an insert 36, arecess 28 can extend from heel portion 24 to forefoot portion 20. Incertain aspects, the rear surface 32 of recess 28 is curved tosubstantially follow the contour of the rear of heel portion 24 and thefront surface 34 of recess 28 extends transversely across first portion26.

As seen best in FIG. 3, a ground engaging lower surface 44 of firstportion 26 includes a plurality of projections 46. Each projection 46 issurrounded by a groove 48. A plurality of transverse slots 50 are formedin lower surface 44, extending between adjacent projections 46. Alongitudinal slot 52 extends along lower surface 44 from heel portion 26to forefoot portion 20.

FIGS. 4 and 5 show bottom and top views of an insert 60 which can beused in a sole component as described herein. Insert 60 is similar toinsert 36, but as illustrated in FIGS. 4 and 5, insert 60 is formed oftwo types of materials 62 and 64, where at least one of the materials isarticle made using the disclosed methods as described herein. FIG. 4shows a bottom view of insert 60, while FIG. 5 shows a top view ofinsert 60 formed of two types of materials 62 and 64, with the insertplaced inside a first portion 66 to form a sole component 14. Insertswith more than two types of materials, at least one of which is articlemade using the disclosed methods as described herein, can also be used.In the example illustrated in FIGS. 4 and 5, a portion of a firstmaterial 62 can be used in the heel region of the insert, and a portionof a second material 64 can be used in the toe region of the insert. Ahigher density material can be used to support the heel region, while alower density material can be used to support the toe region. Forexample, the density of the first material can be at least 0.02 g/cm³greater than the density of the second material. The shape of theportions of the two materials 62 and 64 of the insert can be anysuitable shape. For example, the heel region can be in the shape of awedge. Inserts formed of two types of materials can be useful in runningshoes, as well as in basketball shoes.

Composite Elements

As mentioned above, a disclosed composite element includes a textilehaving one or more fibers, filaments, or yarns, such that the pluralityof fibers, filaments, or yarns comprise a first thermoplastic material;and a second thermoplastic material surrounding the plurality of fibers,filaments, or yarns of the textile and consolidating at least a portionof the textile, wherein the second thermoplastic material has a meltingtemperature lower than a melting temperature of the first thermoplasticmaterial.

Exemplary disclosed composite elements 100 are shown as cross-sectionalplan views in FIGS. 6A-6E, which although depicted in the drawings ashaving certain relative proportions, it is to be understood that thedrawings are not necessarily to scale and that other relativeproportions of element thicknesses, size, spatial relationships, and thelike are within the scope of the drawings. All such modifications andvariations are intended to be included herein within the scope of thiscomposite element shown. Briefly, the various composite elements 100depicted comprise one or more textile 120, 121, 122, 123, and/or 124, inwhich the textile has a plurality of fibers in which the plurality offibers comprise a first thermoplastic material, and the textile isarranged within the composite element such that a second thermoplasticmaterial 120 surrounds the plurality of fibers and consolidates thetextile.

In some instances, as shown in FIG. 6A, a composite element 100 cancomprise a non-woven textile 120 comprising a plurality fibers, with thenon-woven textile 120 arranged or distributed within the compositeelement 100 and in contact with a second thermoplastic material thatsurrounds and consolidates the textile 120. Although the non-woven 120is depicted in FIG. 6A is depicted as having an overall thickness thatis relatively thick compared to the overall thickness of the compositeelement 100, and with the plurality of fibers in the non-woven textileas being loosely bonded and arranged relative to one another, otherarrangements and relative thicknesses are within the scope contemplatedby FIG. 6A. For example, the non-woven textile have a relatively thinnerthickness with the fibers in the non-woven textile is more compressedwith a tighter arrangement of fibers as depicted in FIG. 6B. In otherinstances, as shown in FIG. 6C, a composite element 100 can comprise atextile 120, in which the textile can be a woven or knit textilecomprising a plurality fibers, having the plurality of filaments oryarns comprising a first thermoplastic material, and in which a secondthermoplastic material surrounds the plurality of fibers andconsolidates the textile. The textile 120 depicted in FIG. 6C can be anytextile as disclosed herein, e.g., a woven textile or a knit textile.Alternatively, as shown in FIG. 6D, a composite element comprises afirst textile 121, e.g., a woven or knit textile, and a second textile122, e.g., a woven or knit textile, each textile having a plurality offilaments or yarns in which the plurality of filaments or yarns comprisea first thermoplastic material, and in which a second thermoplasticmaterial surrounds the plurality of fibers and consolidates the textile.It is to be understood that the first textile 121 and the second textile122 do not need to be the same textile, that is, each can independentlybe a woven or knit textile comprising the same or different filaments oryarns. Moreover, the first textile 121 and the second textile 122 canboth comprise the first thermoplastic material, but is also possiblethat the first textile 121 and the second textile 122 can independentlycomprise the first thermoplastic material and an additionalthermoplastic material. In a further instance, as shown in FIG. 6E, acomposite element can comprise a plurality of textiles 150, e.g., asshown a first textile 121, a second textile 122, a third textile 123,and a fourth textile 124, with each textile independently a woven orknit textile and each textile having a plurality of filaments or yarnsin which the plurality of filaments or yarns can comprise a firstthermoplastic material, and in which a second thermoplastic materialsurrounds the plurality of fibers and consolidates the textile.Similarly to the composite element described in FIG. 6D, it isunderstood that the plurality of textiles can each comprise the firstthermoplastic material, but is also possible that the plurality oftextiles can independently comprise the first thermoplastic material oran additional thermoplastic material. Although in FIGS. 6D and 6E, theplurality of textiles are shown with a certain relative spacing and acertain thickness of the second thermoplastic material between eachtextile of the plurality of textiles, it is also contemplated that eachtextile of the plurality of textiles can have relatively little orsubstantially no spacing between each textile of the plurality oftextiles or such that each textile of the plurality of textiles one faceof a textile is contacting, in part or in whole, the opposing face ofthe textile above and/or below it. As shown in FIGS. 6A-6E, it can beappreciated that the second thermoplastic material can be found betweenand within the fibers, filaments, or yarns of the textile 120, 121, 122,123, and/or 124. That is, the second thermoplastic material can be in amolten or melted state that is flowable, allowing flow of the secondthermoplastic material between and within the fibers, filaments, oryarns of the textile 120, 121, 122, 123, and/or 124, followed bysolidification of the second thermoplastic material.

Moreover, it is understood that in any of composite elements asdisclosed, e.g., in each of FIGS. 6A-6E, that a fiber, filament or yarncomprising a first thermoplastic material means that the fiber, filamentor yarn may comprising substantially, at least in terms of polymercontent, only a single thermoplastic material, but is also inclusive ofcomposite elements in which the fiber, filament or yarn comprises thefirst thermoplastic material a plurality of thermoplastic materials asdisclosed herein. Similarly, disclosure of a second thermoplasticmaterial is inclusive of composite elements in which the secondthermoplastic material is substantially, at least in terms of polymercontent, only a single thermoplastic material, as well as compositeelements in which the second thermoplastic material comprises aplurality of thermoplastic materials as disclosed herein.

As discussed herein below, it is understood the textile can include aplurality of fibers, a plurality of filaments, or a plurality of yarns,such that the plurality of fibers, the plurality of filaments, or theplurality of yarns comprise a first thermoplastic material. In someinstances, the plurality of fibers, the plurality of filaments, or theplurality of yarns can have a first and a second fiber, a first filamentand a second filament, or a first yarn and a second yarn, such that eachof the first and the second fiber, filament, or yarn, independently havea first thermoplastic material and an additional thermoplastic materialas disclosed herein. For example, a textile can have a plurality ofyarns, such that the first yarn comprises a first thermoplastic materialand the second yarn comprises a thermoplastic material that is not thefirst thermoplastic material, but another thermoplastic material asdisclosed herein. That is, the first thermoplastic material and theadditional thermoplastic material can be the same or different in termsof polymer composition or a property, e.g., melting temperature of thepolymer.

A further composite element is described by the drawing in FIG. 7, inwhich the composite element comprises a spacer textile 160, in which thetextile has a first textile face 131, a second textile face 132, and aspacer yarns 135. The connecting yarns 135 form a connection between thefirst textile face 131 and the second textile face 132, and the spaceryarns can be arranged to form greater or lesser spacing between thefirst textile face 131 and the second textile face 132. As shown, thesecond thermoplastic material can be found between and within the firsttextile face 131, the second textile face 132, and the spacer yarns 135.That is, the second thermoplastic material can be in a molten or meltedstate that is flowable, allowing flow of the second thermoplasticmaterial between and within the first textile face 131, the secondtextile face 132, and the spacer yarns 135, followed by solidificationof the second thermoplastic material.

In some instances, a disclosed composite element includes a textilehaving a plurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and a second thermoplastic material surroundingthe plurality of fibers of the textile and consolidating at least aportion of the textile, wherein the second thermoplastic material has amelting temperature lower than a melting temperature of the firstthermoplastic material.

In other instances, a disclosed composite element includes a textilehaving a plurality of filaments, the plurality of filaments comprising afirst thermoplastic material; and a second thermoplastic materialsurrounding the plurality of fibers of the textile and consolidating atleast a portion of the textile, wherein the second thermoplasticmaterial has a melting temperature lower than a melting temperature ofthe first thermoplastic material.

In further instances, a disclosed composite element includes a textilehaving at least one yarn, the at least one yarn comprising a firstthermoplastic material; and a second thermoplastic material surroundingthe plurality of fibers of the textile and consolidating at least aportion of the textile, wherein the second thermoplastic material has amelting temperature lower than a melting temperature of the firstthermoplastic material.

Fluid Chambers

In accordance with some aspects, the composite element can be affixed onto a components, e.g., a fluid chamber such as may be incorporate into asole of an article of footwear.

In some aspects, the present disclosure pertains to a fluid chamber,comprising: a composite element extending across and affixed to at leasta portion of the first side of the fluid chamber, to the second side ofthe fluid chamber, to the sidewall of the fluid chamber, or to anycombination thereof; wherein the composite element comprises a textileincluding a plurality of fibers, the plurality of fibers comprising afirst thermoplastic material, and a second thermoplastic materialsurrounding and the plurality of fibers in the textile and consolidatingthe textile, the second thermoplastic material having a meltingtemperature lower than a melting temperature of the first thermoplasticmaterial; and a fluid chamber having a first side, a second side, and asidewall extending between the first side and the second side, the fluidchamber comprising a third thermoplastic material.

In other aspects, the fluid chamber is as described herein, but withouta composite element disposed on or part of the fluid chamber itself.

The fluid chamber can be unfilled, partially inflated, or fully inflatedwhen the composite element is affixed to the fluid chamber. The fluidchamber is a fluid chamber capable of including a volume of a fluid. Anunfilled fluid chamber is a fluid-fillable fluid chamber and a filledfluid chamber which has been at least partially inflated with a fluid ata pressure equal to or greater than atmospheric pressure. When disposedonto or incorporated into an article, the fluid chamber is generally, atthat point, a fluid-filled fluid chamber. The fluid be a gas or aliquid. The gas can include air, nitrogen gas (N₂), or other appropriategas.

The fluid chamber can have a gas transmission rate for nitrogen gas, forexample, where a fluid chamber wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the fluid chamberdescribed herein. The fluid chamber can have a first fluid chamber wallhaving a first fluid chamber wall thickness (e.g., about 0.1 to 40mils). The fluid chamber can have a first fluid chamber wall that canhave a gas transmission rate (GTR) for nitrogen gas of less than about15 cm³/m²·atm·day, less than about 10 m³/m²·atm·day, less than about 5cm³/m²·atm·day, less than about 1 cm³/m²·atm·day (e.g., from about 0.001cm³/m²·atm·day to about 1 cm³/m²·atm·day, about 0.01 cm³/m²·atm·day toabout 1 cm³/m²·atm·day or about 0.1 cm³/m²·atm·day to about 1cm³/m²·atm·day) for an average wall thickness of 20 mils. The fluidchamber can have a first fluid chamber wall having a first fluid chamberwall thickness, where the first fluid chamber wall has a gastransmission rate of 15 cm³/m²·atm·day or less for than nitrogen for anaverage wall thickness of 20 mils.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated fluid chambers is ASTM D-1434-82-V. See, e.g.,U.S. Pat. No. 6,127,026, which is incorporated by reference as if fullyset forth herein. According to ASTM D-1434-82-V, permeance, permeabilityand diffusion are measured by the following formulae:

(quantity of gas)/[(area)×(time)×(pressure difference)]=permeance(GTR)/(pressure difference)=cm³/m²·atm·day (i.e., 24 hours)  Permeance

[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²·atm·day (i.e., 24 hours)  Permeability

(quantity of gas)/[(area)×(time)]=GTR=cm³/m²·day (i.e., 24hours)  Diffusion at one atmosphere

In some embodiments, a fluid chamber can comprise a composite elementextending across and affixed to at least a portion of the first side ofthe fluid chamber, to the second side of the fluid chamber, to thesidewall of the fluid chamber, or to any combination thereof; whereinthe composite element comprises a textile including a plurality offibers, the plurality of fibers comprising a first thermoplasticmaterial, and a second thermoplastic material surrounding and theplurality of fibers in the textile and consolidating the textile, thesecond thermoplastic material having a melting temperature lower than amelting temperature of the first thermoplastic material; and a fluidchamber having a first side, a second side, and a sidewall extendingbetween the first side and the second side, the fluid chamber comprisinga third thermoplastic material.

The fluid chamber can include a layered film including at least onepolymeric layer or at least two or more polymeric layers. Each of thepolymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can be formed of polymer material such as athermoplastic material. The thermoplastic material can include anelastomeric material, such as a thermoplastic elastomeric material. Thethermoplastic materials can include thermoplastic polyurethane (TPU),such as those described herein. The thermoplastic materials can includepolyester-based TPU, polyether-based TPU, polycaprolactone-based TPU,polycarbonate-based TPU, polysiloxane-based TPU, or combinationsthereof. Non-limiting examples of thermoplastic material that can beused include: “PELLETHANE” 2355-85ATP and 2355-95AE (Dow ChemicalCompany of Midland, Mich., USA), “ELASTOLLAN” (BASF Corporation,Wyandotte, Mich., USA) and “ESTANE” (Lubrizol, Brecksville, Ohio, USA),all of which are either ester or ether based. Additional thermoplasticmaterial can include those described in U.S. Pat. Nos. 5,713,141;5,952,065; 6,082,025; 6,127,026; 6,013,340; 6,203,868; and 6,321,465,which are incorporated herein by reference.

The polymeric layer can be formed of one or more of the following:ethylene-vinyl alcohol copolymers (EVOH), poly(vinyl chloride),polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride),polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g.,acrylonitrile-methyl acrylate copolymers), polyurethane engineeringplastics, polymethylpentene resins, ethylene-carbon monoxide copolymers,liquid crystal polymers, polyethylene terephthalate, polyether imides,polyacrylic imides, and other polymeric materials known to haverelatively low gas transmission rates. Blends and alloys of thesematerials as well as with the TPUs described herein and optionallyincluding combinations of polyimides and crystalline polymers, are alsosuitable. For instance, blends of polyimides and liquid crystalpolymers, blends of polyamides and polyethylene terephthalate, andblends of polyamides with styrenics are suitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, Ohio, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, Tex., USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, Del., USA);polyvinylidene chloride available from S. C. Johnson (Racine, Wis., USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, Tex., USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can be formed of a thermoplasticmaterial which can include a combination of thermoplastic polymers. Inaddition to one or more thermoplastic polymers, the thermoplasticmaterial can optionally include a colorant, a filler, a processing aid,a free radical scavenger, an ultraviolet light absorber, and the like.Each polymeric layer of the film can be made of a different ofthermoplastic material including a different type of thermoplasticpolymer.

The fluid chamber can be made by applying heat, pressure and/or vacuumto a film. The fluid chamber (e.g., one or more polymeric layers) can beformed using one or more polymeric materials, and forming the fluidchamber using one or more processing techniques including, for example,extrusion, blow molding, injection molding, vacuum molding, rotarymolding, transfer molding, pressure forming, heat sealing, casting,low-pressure casting, spin casting, reaction injection molding, radiofrequency (RF) welding, and the like. The fluid chamber can be made byco-extrusion followed by heat sealing or welding to give an inflatablefluid chamber, which can optionally include one or more valves (e.g.,one way valves) that allows the fluid chamber to be filled with thefluid (e.g., gas).

Cushioning Structures

In accordance with some aspects, the composite element can be affixed onto a component, e.g., a cushioning structure such as may be incorporatedinto a sole of an article of footwear. Thus, in various aspects, thepresent disclosure pertains to a cushioning structure comprising: afirst cushioning element; and a composite element affixed to thecushioning element, wherein the composite element comprises a textileincluding a plurality of fibers, the plurality of fibers comprising afirst thermoplastic material; and a second thermoplastic material,wherein the second thermoplastic material has a melting temperaturelower than a melting temperature of the first thermoplastic material;wherein, in the composite element, the second thermoplastic materialsurrounds the plurality of fibers in the textile and consolidates thetextile. In some instances, the cushioning element can be a fluidchamber. In other instances, the cushioning element can be a foamcomponent.

Exemplary cushioning structures are depicted in FIGS. 8A-8B, ascross-sectional plan views of disclosed cushioning structures comprisinga first cushioning element that is a fluid chamber and a disclosedcomposite element. For example, as shown in FIG. 8A, a cushioningstructure 500 can comprise a first cushioning element that is a fluidchamber 200 in which the fluid chamber has an internally-facing side andan externally-facing side opposite the internally-facing side, and thecomposite element 100, comprising a textile 121 including a plurality offibers, the plurality of fibers comprising a first thermoplasticmaterial; and a second thermoplastic material 110, such that thecomposite element 100 is affixed to the internally-facing side of thefluid chamber 200. In another instance, as shown in FIG. 8B, acushioning structure 510 can comprise a first cushioning element that isa fluid chamber 200 in which the fluid chamber has an internally-facingside and an externally-facing side opposite the internally-facing side,and the composite element 100, comprising a textile 121 including aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and a second thermoplastic material 110, suchthat the composite element 100 is affixed to the externally-facing sideof the fluid chamber 200.

Further exemplary cushioning structures are depicted in FIGS. 9A-9B, ascross-sectional plan views of disclosed cushioning structures comprisinga one or more cushioning elements that are foam components and adisclosed composite element. For example, as shown in FIG. 9A, acushioning structure 600 can comprise a first cushioning element that isa foam component 310 and a second cushioning element that is a foamcomponent 320, in which each of the first cushioning elements 310 andsecond cushioning elements 320, each being a foam component, have aninternally-facing side and an externally-facing side opposite theinternally-facing side, and the composite element 100, comprising atextile 121 including a plurality of fibers, the plurality of fiberscomprising a first thermoplastic material; and a second thermoplasticmaterial 110, such that the composite element 100 is affixed to theexternally-facing side of each of the first cushioning elements 310 andsecond cushioning elements 320, each being a foam component as shown inFIG. 9A. In another instance, as shown in FIG. 9B, a cushioningstructure 610 can comprise a first cushioning element that is a foamcomponent 300 in which the foam component has two externally-facingsides as shown, and the composite element 100, comprising a textile 121including a plurality of fibers, the plurality of fibers comprising afirst thermoplastic material; and a second thermoplastic material 110,such that the composite element 100 is affixed to one of theexternally-facing sides of the foam component 300.

The cushioning element, e.g., a first cushioning element, can have aninternally-facing side and an externally-facing side opposite theinternally-facing side, and the composite element can be affixed to theinternally-facing side. Alternatively, the cushioning element has aninternally-facing side and an externally-facing side opposite theinternally-facing side, and the composite element can be affixed to theexternally-facing side. In some cases, the externally-facing side of thecushioning structure can further have an outer layer affixed to a sideof the composite element opposite the side affixed to theexternally-facing side of the cushioning element. The cushioningstructure can be a cushioning structure for an article of footwear, suchthat the internally-facing side is an upper-facing side, theexternally-facing side is a ground-facing side, and the outer layer isan outsole layer.

It is to be understood that the cushioning structure as described hereinabove can further include a second cushioning element, and the compositeelement is positioned between and affixed to both the first cushioningelement and the second cushioning element. In some cases, it may beuseful to for the first cushioning element to be a foam component or afluid chamber, and the second cushioning element is a foam component ora fluid chamber. In specific instances, the first cushioning element canbe a foam component, and the second cushioning element can be a fluidchamber. In other specific instances, the first cushioning element canbe a fluid chamber, and the second cushioning element can be a foamcomponent.

The cushioning structure described herein can have the first cushioningelement as a fluid chamber having a first side, a second side, and asidewall extending between the first side, wherein the composite elementextends across and is affixed to at least a portion of the first side ofthe fluid chamber, to the second side of the fluid chamber, to thesidewall of the fluid chamber, or to any combination thereof. In somecases, in the first side of the fluid chamber and at least a portion ofthe sidewall are formed of a first sheet having a third thermoplasticmaterial, the second side of the fluid chamber is formed of a secondsheet having a fourth thermoplastic material. It is understood that thecushioning structure herein throughout can utilize any disclosedcomposite element.

In various aspects, a cushioning structure can be a disclosed fluid. Thecushioning structure disclosed herein can be used in a variety ofarticles. For example, a disclosed cushioning structure can be acushioning structure for an article of apparel. Other non-limitingexamples of a disclosed cushioning structure is a cushioning structurefor an article of sporting equipment. In some specific uses, a disclosedcushioning structure can be a sole structure for an article of footwear.

The disclosed cushioning can further have an outsole having achamber-engaging side and a ground-engaging side, wherein thechamber-engaging side of the outsole covers and is affixed to at least aportion of the ground-facing side of the fluid chamber. It may be usefulfor the chamber-engaging side of the outsole to be affixed to at least aportion of the sidewall of the fluid chamber. An outsole can include asecond composite element between the chamber-engaging side of theoutsole and a portion of the ground-facing side of the fluid-filledchamber. In other instances, an outsole can include a second compositeelement between the chamber-engaging side of the outsole and a portionof the ground-facing side of the fluid-filled chamber. It is understoodthat a second composite element can be any disclosed composite element.In some instances, a disclosed cushioning can further have a mid-solehaving a ground-facing side affixed to the second side of the fluidchamber.

Processes for Manufacturing

The present disclosure provides for a method of manufacturing acomposite element, the method comprising: positioning a textile and filmadjacent to each other, wherein the textile includes a plurality offibers, the plurality of fibers comprising a first thermoplasticmaterial; and wherein the film comprises a second thermoplastic materialhas a melting temperature lower than a melting temperature of the firstthermoplastic material; and increasing a temperature of the film to atemperature at or above the melting temperature of the secondthermoplastic material but below the melting temperature of the firstthermoplastic material, such that the second thermoplastic flows andsurrounds the plurality of fibers of the textile and consolidates thetextile; and decreasing the temperature of the film to a temperaturebelow the melting temperature of the second thermoplastic material suchthat the second thermoplastic re-solidifies, forming the compositeelement.

The present disclosure also provides for a method of forming a fluidchamber, the method comprising: affixing a composite element to a fluidchamber, wherein the fluid chamber has a first side, a second side, anda sidewall extending between the first side and the second side, and thefluid chamber comprises a third thermoplastic material; wherein thecomposite element extends across and affixed to at least a portion ofthe first side of the fluid chamber, to the second side of the fluidchamber, to the sidewall of the fluid chamber, or to any combinationthereof, and wherein the composite element comprises a textile includinga plurality of fibers, the plurality of fibers comprising a firstthermoplastic material, and a second thermoplastic material surroundingand the plurality of fibers in the textile and consolidating thetextile, the second thermoplastic material having a melting temperaturelower than a melting temperature of the first thermoplastic material.

The present disclosure further provides for a method of making acushioning structure, the method comprising: affixing a compositeelement to a first cushioning element; wherein the composite elementcomprises a textile including a plurality of fibers, the plurality offibers comprising a first thermoplastic material; a second thermoplasticmaterial, wherein the second thermoplastic material has a meltingtemperature lower than a melting temperature of the first thermoplasticmaterial; and, in the composite element, the second thermoplasticmaterial surrounds the plurality of fibers in the textile andconsolidates the textile.

The present disclosure also provides for a method of manufacturing anarticle, comprising: affixing a first component to a cushioningstructure, wherein the cushioning structure is a disclosed cushioningstructure.

Thermoplastic Polymeric Materials

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, primer layer, coating, and like the.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, primer layer, coating, and like the. The polymer can bea thermoplastic polymer. The polymer can be an elastomeric polymer suchas a thermoplastic elastomeric polymer. The polymer can be selectedfrom: polyurethanes (including thermoplastic polyurethanes (TPUs) andelastomeric TPUs), polyesters, polyethers, polyamides, vinyl polymers(e.g., copolymers of vinyl alcohol, vinyl esters, ethylene, acrylates,methacrylates, styrene, and so on), polyacrylonitriles, polyphenyleneethers, polycarbonates, polyureas, polystyrenes, co-polymers thereof(including polyester-polyurethanes, polyether-polyurethanes,polycarbonate-polyurethanes, polyether block polyamides (PEBAs), andstyrene block copolymers), and any combination thereof, as describedherein. The polymer can include one or more polymers selected from thegroup consisting of polyesters, polyethers, polyamides, polyurethanes,polyolefins copolymers of each, and combinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to on the basisof the name of the functional group present in the segment (e.g., apolyether segment, a polyester segment), as well as based on the name ofthe chemical structure which was reacted in order to form the segment(e.g., a polyol-derived segment, an isocyanate-derived segment). Whenreferring to segments of a particular functional group or of aparticular chemical structure from which the segment was derived, it isunderstood that the polymer can contain up to 10 mole percent ofsegments of other functional groups or derived from other chemicalstructures. For example, as used herein, a polyether segment isunderstood to include up to 10 mole percent of non-polyether segments.

In aspects, exemplary thermoplastic polymers include homo-polymers andco-polymers. In certain aspects, the thermoplastic polymer can be arandom co-polymer. In one aspect, the thermoplastic polymer can be ablock co-polymer. The term “polymer” refers to a polymerized moleculehaving one or more monomer species, and includes homopolymers andcopolymers. The term “copolymer” refers to a polymer having two or moremonomer species, and includes terpolymers (i.e., copolymers having threemonomer species). For example, the thermoplastic polymer can be a blockco-polymer having repeating blocks of polymeric units of the samechemical structure (segments) which are relatively harder (hardsegments), and repeating blocks of polymeric segments which arerelatively softer (soft segments). In various aspects, in blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within the blocksor between the blocks or both within and between the blocks. Particularexamples of hard segments include isocyanate segments and polyamidesegments. Particular examples of soft segments include polyethersegments and polyester segments. As used herein, the polymeric segmentcan be referred to as being a particular type of polymeric segment suchas, for example, an isocyanate segment, a polyamide segment, a polyethersegment, a polyester segment, and the like. It is understood that thechemical structure of the segment is derived from the described chemicalstructure. For example, an isocyanate segment is a polymerized unitincluding an isocyanate functional group. When referring to a block ofpolymeric segments of a particular chemical structure, the block cancontain up to 10 mol % of segments of other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mol % of non-polyether segments.

In general, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm³/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megapascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

Thermoplastic Polyurethanes

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Additionally, polyurethane can be anelastomeric polyurethane such as a thermoplastic elastomericpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R₁ group and R₂ group independently is an aliphatic or aromaticgroup. Optionally, each R₂ can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R₃ includes the chain extender.As with each R₁ and R₃, each R₃ independently is an aliphatic oraromatic functional group.

Each R₁ group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R₁ group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R₁ groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R₁group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term C_(n) itmeans the alkene or alkylene group has “n” carbon atoms. For example,C₁₋₆ alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5,or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R₁ group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H₁₂ aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H₁₂aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R₃ group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R₂ group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R₂ group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R₂ group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term C_(n) it means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R₂ group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol-1,5,diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R₂ group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol-1,5, diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R₂ group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R₂ is an aliphatic or aromatic group having pendant amino,carboxylate, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R₂ group in the polyurethane can include apolytetramethylene oxide group. At least one R₂ group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R₂ group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R₂ of the polyurethane can be a polysiloxane, In thesecases, the R₂ group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R₅ independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R₄ group can independently be an H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R₄ group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R₅ group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R₅ group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R₅ group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). This crosslinked polymericnetwork can be produced by polymerizing one or more isocyanates with oneor more polyamino compounds, polysulfhydryl compounds, or combinationsthereof, as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R₁ group in Formula 1, and the R₁ and R₃ groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R₂ group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane is composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, Ill., USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

One or more of the polyurethanes (e.g., those used in the primer as thecoating (e.g., water-dispersible polyurethane)) can be produced bypolymerizing one or more isocyanates with one or more polyols to producecopolymer chains having carbamate linkages (—N(C═O)O—) and one or morewater-dispersible enhancing moieties, where the polymer chain includesone or more water-dispersible enhancing moieties (e.g., a monomer inpolymer chain). The water-dispersible polyurethane can also be referredto as “a water-borne polyurethane polymer dispersion.” Thewater-dispersible enhancing moiety can be added to the chain of Formula1 or 2 (e.g., within the chain and/or onto the chain as a side chain).Inclusion of the water-dispersible enhancing moiety enables theformation of a water-borne polyurethane dispersion. The term“water-borne” herein means the continuous phase of the dispersion orformulation of about 50 weight percent to 100 weight percent water,about 60 weight percent to 100 weight percent water, about 70 weightpercent to 100 weight percent water, or about 100 weight percent water.The term “water-borne dispersion” refers to a dispersion of a component(e.g., polymer, cross-linker, and the like) in water withoutco-solvents. The co-solvent can be used in the water-borne dispersionand the co-solvent can be an organic solvent. Additional detailregarding the polymers, polyurethanes, isocyanates and the polyols areprovided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (HO)_(x)Q(COOH)_(y), where Q can be a straight orbranched bivalent hydrocarbon radical containing 1 to 12 carbon atoms,and x and y can each independently be 1 to 3. Illustrative examplesinclude dimethylolpropanoic acid (DMPA), dimethylol butanoic acid(DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malicacid, dihydroxymalic acid, dihydroxytartaric acid, and the like, andmixtures thereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281. Additional typesof water-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Thermoplastic Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide.The polyamide can be an elastomeric polyamide such as a thermoplasticelastomeric polyamide. The polyamide can be a polyamide homopolymerhaving repeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a co-polyamide, or can be a random co-polyamide. Thecopolyamide can be formed from the polycodensation of a polyamideoligomer or prepolymer with a second oligomer prepolymer to form acopolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R₆ group represents the portion of thepolyamide derived from the lactam or amino acid.

The R₆ group can be derived from a lactam. The R₆ group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R₆ group can be derived from caprolactam orlaurolactam. The R₆ group can be derived from one or more amino acids.The R₆ group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R₆ groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R₇ group represents the portion of thepolyamide derived from the diamino compound, and the R₈ group representsthe portion derived from the dicarboxylic acid compound:

The R₇ group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R₇ group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD), m-xylylene diamine (MXD), and1,5-pentamine diamine. The R₈ group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR₈ can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R₈ can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryl lactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH₂)₁₀—COOH can be used; and a lactam such as caprolactam andlauryl lactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryl lactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be acrylic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked thorough interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies.

Thermoplastic Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester. Additionally, the polyester can be anelastomeric polyester such as a thermoplastic polyester. The polyestercan be formed by reaction of one or more carboxylic acids, or itsester-forming derivatives, with one or more bivalent or multivalentaliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol.The polyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycodensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1-3 propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenaphthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(α-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Thermoplastic Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin. Additionally, thepolyolefin can be an elastomeric polyolefin such as a thermoplasticelastomeric polyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monoolefins and diolefins copolymerized with a vinyl,acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/orvinyl acetate. Polyolefin copolymers comprising vinyl acetate-derivedunits can be a high vinyl acetate content copolymer, e.g., greater thanabout 50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonoolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monoolefins monomers or acopolymer of a suitable monoolefins monomer and a vinyl monomer.Exemplary polyolefin copolymers include ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic can further comprise one or more processing aids. Theprocessing aid can be a non-polymeric material. These processing aidscan be independently selected from the group including, but not limitedto, curing agents, initiators, plasticizers, mold release agents,lubricants, antioxidants, flame retardants, dyes, pigments, reinforcingand non-reinforcing fillers, fiber reinforcements, and lightstabilizers.

Thermoplastic Additives

In some aspects, a disclosed thermoplastic polymer or a disclosed fiber,filament, yarn, film, sheet or textile comprising a thermoplasticpolymer can further comprise an additive. The additive can beincorporated directly into a fiber, filament, yarn, film, sheet ortextile or alternatively, applied thereto. In addition, an additive canbe incorporated into a polymer melt prior to extrusion, forming a sheetor film, and polymer blends. Additives that can be used in the disclosedthermoplastic polymers, fibers, filaments, yarns, or fabrics include,but are not limited to, dyes, pigments, colorants, ultraviolet lightabsorbers, hindered amine light stabilizers, antioxidants, processingaids or agents, plasticizers, lubricants, emulsifiers, pigments, dyes,optical brighteners, rheology additives, catalysts, flow-control agents,slip agents, crosslinking agents, crosslinking boosters, halogenscavengers, smoke inhibitors, flame-proofing agents, antistatic agents,fillers, or mixtures of two or more of the foregoing. When used, anadditive can be present in an amount of from about 0.01 wt % to about 10wt %, about 0.025 wt % to about 5 wt %, or about 0.1 wt % to 3 wt %,where the wt % is based upon the sum of the material components in thethermoplastic composition, fiber, filament, yarn, or fabric.

Individual components can be mixed together with the other components ofthe thermoplastic composition in a continuous mixer or a batch mixer,e.g., in an intermeshing rotor mixer, such as an Intermix mixer, a twinscrew extruder, in a tangential rotor mixer such as a Banbury mixer,using a two-roll mill, or some combinations of these to make acomposition comprising a thermoplastic polymer and an additive. Themixer can blend the components together via a single step or multiplesteps, and can mix the components via dispersive mixing or distributivemixing to form the resulting thermoplastic composition. This step isoften referred to as “compounding.”

In some aspects, the additive is an antioxidant such as ascorbic acid,an alkylated monophenol, an alkylthiomethylphenol, a hydroquinone oralkylated hydroquinone, a tocopherol, a hydroxylated thiodiphenyl ether,an alkylidenebisphenol, a benzyl compound, a hydroxylated malonate, anaromatic hydroxybenzl compound, a triazine compound, abenzylphosphonate, an acylaminophenol, an ester ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, an ester ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols, an ester ofβ-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- orpolyhydric alcohols, an ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, an amide ofβ-(3,5-di-tert-butyl-4-hydromhenyl)propionic acid, an aminicantioxidant, or mixtures of two or more of the foregoing.

Exemplary alkylated monophenols include, but are not limited to,2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-ethylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol, and mixtures of two or moreof the foregoing.

Exemplary alkylthiomethylphenols include, but are not limited to,2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures of two or more ofthe foregoing.

Exemplary hydroquinones and alkylated hydroquinones include, but are notlimited to, 2,6-di-tert-butyl-4-methoxyphenol,2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone,2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyphenyl stearate,bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate, and mixtures of two ormore of the foregoing.

Exemplary tocopherols include, but are not limited to, α-tocopherol,p-tocopherol, 7-tocopherol, 6-tocopherol, and mixtures of two or more ofthe foregoing.

Exemplary hydroxylated thiodiphenyl ethers include, but are not limitedto, 2,2′-thiobis(6-tert-butyl-4-methylphenol),2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide, and mixtures of two ormore of the foregoing.

Exemplary alkylidenebisphenols include, but are not limited to,2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2.2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, andmixtures of two or more of the foregoing.

Exemplary benzyl compounds include, but are not limited to,3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, andmixtures of two or more of the foregoing.

Exemplary hydroxybenzylated malonates include, but are not limited to,dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-ethylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,and mixtures of two or more of the foregoing.

Exemplary aromatic hydroxybenzl compounds include, but are not limitedto,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixtures of twoor more of the foregoing.

Exemplary triazine compounds include, but are not limited to,2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1.3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and mixturesof two or more of the foregoing.

Exemplary benzylphosphonates include, but are not limited to,dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures of two ormore of the foregoing.

Exemplary acylaminophenols include, but are not limited to,4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide,2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine andoctyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate, and mixtures oftwo or more of the foregoing.

Exemplary esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,include, but are not limited to esters with a mono- or polyhydricalcohol such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesof esters derived from two or more of the foregoing mono- or polyhydricalcohols.

Exemplary esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionicacid, include, but are not limited to esters with a mono- or polyhydricalcohol such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesof esters derived from two or more of the foregoing mono- or polyhydricalcohols.

Exemplary esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid,include, but are not limited to esters with a mono- or polyhydricalcohol such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesof esters derived from two or more of the foregoing mono- or polyhydricalcohols.

Exemplary esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid,include, but are not limited to esters with a mono- or polyhydricalcohol such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesof esters derived from two or more of the foregoing mono- or polyhydricalcohols.

Exemplary amides of β-(3,5-di-tert-butyl-4-hydromhenyl)propionic acid,include, but are not limited to,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide,and mixtures of two or more of the foregoing.

Exemplary aminic antioxidants include, but are not limited to,N,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine.phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol,and mixtures of two or more of the foregoing.

In some aspects, the additive is a UV absorber and/or light stabilizer,including, but limited to, a 2-(2-hydroxyphenyl)-2H-benzotriazolecompound, a 2-hydroxybenzophenone compound, an ester of a substitutedand unsubstituted benzoic acid, an acrylate or malonate compound, asterically hindered amine stabilizer compound, an oxamide compound, atris-aryl-o-hydroxyphenyl-s-triazine compound, or mixtures of two ormore of the foregoing.

Exemplary 2-(2-hydroxyphenyl)-2H-benzotriazole compounds include, butare not limited to, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-a-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-(ω)-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole.5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,and mixtures of two or more of the foregoing.

Exemplary 2-hydroxybenzophenone compounds include, but are not limitedto, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy,4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxyderivatives of 2-hydroxybenzophenone, and mixtures of two or more suchderivatives.

Exemplary esters of a substituted and unsubstituted benzoic acidinclude, but are not limited to, 4-tertbutyl-phenyl salicylate, phenylsalicylate, octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, and mixtures of two or more of theforegoing.

Exemplary an acrylate or malonate compounds include, but are not limitedto, α-cyano-β,β-diphenylacrylic acid ethyl ester or isooctyl ester,α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, dimethylp-methoxybenzylidenemalonate,di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate,and mixtures of two or more of the foregoing.

Exemplary sterically hindered amine stabilizer compounds include, butare not limited to, 4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2.2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarateand2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine,and mixtures of two or more of the foregoing.

Exemplary oxamide compounds include, but are not limited to,4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides, and mixtures of two or more of theforegoing.

Exemplary tris-aryl-o-hydroxyphenyl-s-triazine compounds include, butare not limited to,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenylJ-642-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxy-propyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)-phenyl]-s-triazine},2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyq-s-triazine,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine,4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine, and mixtures oftwo or more of the foregoing.

In some aspects, the additive is a peroxide scavenger such as an esterof β-thiodipropionic acid, e.g., the lauryl, stearyl, myristyl ortridecyl esters, mercaptobenzimidazole, and the zinc salt of2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, ormixtures of any of the foregoing.

In some aspects, the additive is a polyamide stabilizer such as a coppersalt of a halogen, e.g., iodide, and/or phosphorus compounds and saltsof divalent manganese.

In some aspects, the additive is a basic co-stabilizer such as melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acids,for example, calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

In some aspects, the additive is a nucleating agent such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals, ormixtures thereof. Alternatively, the nucleating agent can be a mono- orpolycarboxylic acids, and the salts thereof, e.g., 4-tert-butylbenzoicacid, adipic acid, diphenylacetic acid, sodium succinate, sodiumbenzoate, or mixtures thereof. In a further aspect, the additive can bea nucleating agent comprising both an inorganic and an organic materialas disclosed herein above.

In some aspects, the rheology modifier can be a nano-particles havingcomparatively high aspect ratios, nano-clays, nano-carbon, graphite,nano-silica, and the like.

In some aspects, the additive is a filler or reinforcing agent such asclay, kaolin, talc, asbestos, graphite, glass (such as glass fibers,glass particulates, and glass bulbs, spheres, or spheroids), mica,calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide,silicates, diatomaceous earth, carbonates (such as calcium carbonate,magnesium carbonate and the like), metals (such as titanium, tungsten,zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron,bronze, cobalt, beryllium, and alloys of these), metal oxides (such aszinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide,zirconium oxide and the like), metal hydroxides, particulate syntheticplastics (such as high molecular weight polyethylene, polypropylene,polystyrene, polyethylene ionomeric resins, polyamide, polyester,polyurethane, polyimide, and the like), synthetic fibers (such as fiberscomprising high molecular weight polyethylene, polypropylene,polystyrene, polyethylene ionomeric resins, polyamide, polyester,polyurethane, polyimide, and the like), particulate carbonaceousmaterials (such as carbon black and the like), wood flour and flours orfibers of other natural products, as well as cotton flock, celluloseflock, cellulose pulp, leather fiber, and combinations of any of theabove. Non-limiting examples of heavy-weight filler components that canbe used to increase the specific gravity of the cured elastomercomposition can include titanium, tungsten, aluminum, bismuth, nickel,molybdenum, iron, steel, lead, copper, brass, boron, boron carbidewhiskers, bronze, cobalt, beryllium, zinc, tin, metal oxides (such aszinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide,and zirconium oxide), metal sulfates (such as barium sulfate), metalcarbonates (such as calcium carbonate), and combinations of these.Non-limiting examples of light-weight filler components that can be usedto decrease the specific gravity of the elastomer compound can includeparticulate plastics, hollow glass spheres, ceramics, and hollowspheres, regrinds, and foams, which can be used in combinations.

In some aspects, the additive is a cross-linking agent. There are avariety of cross-linking agents that can be used in the disclosedthermoplastic compositions. For example, a cross-linking agent can be afree-radical initiator. The free radical initiator can generate freeradicals through thermo cleavage or UV radiation. The free-radicalinitiator can be present in an amount from about 0.001 wt % to about 1.0wt %. A variety of radical initiators can be used as the radical sourcesto make thermoplastic compositions have a crosslinked structure.Suitable radical initiators applied include peroxides, sulfurs, andsulfides. Exemplary peroxides include, but are not limited to, aliphaticperoxides and aromatic peroxides, such as diacetylperoxide,di-tert-butypperoxide, dicumyl peroxide, dibenzoylperoxide,2,5-dimethyl-2,5-di(benzoylperoxy)hexane,2,5-dimethyl-2,5-di(butylperoxy)-3-hexyne,2,5-bis-(t-butylperoxy)-2,5-dimethyl hexane,n-butyl-4,4-bis(t-butylperoxyl)valerate,1,4-bis-(t-butylperoxyisopropyl)-benzene, t-butyl peroxybenzoate,1,1-bis-(t-butylperoxy)-3,3,5 tri-methylcyclohexane, anddi(2,4-dichloro-benzoyl), or combinations of two or more of theforegoing.

In some aspects, the additive is a colorant. The term “colorant,” asused herein, means a compound providing color to a substrate, e.g., adisclosed thermoplastic composition. A colorant can include withoutlimitation a dye, a pigment, and the like, and mixtures and combinationsthereof. In some instances, the colorant can be an organic or inorganicpigment, a dye, or mixtures or combinations thereof. In a furtheraspect, the pigment or dye is an inorganic material such as a metaloxide, e.g., iron oxide or titanium dioxide. Alternatively, theinorganic pigment or dye can be a metal compound, e.g., strontiumchromate or barium sulfate, or a metallic pigment, e.g., aluminum flakesor particles. Other exemplary inorganic pigments include carbon black,talc, and the like. In some cases, the metal compound is not onecomprising cadmium. In can be desirable in some instances that theinorganic pigment or dye is not one that contains a lead, cadmium andchromium (VI) compound. In a further aspect, the pigment or dye is anorganic compound such as a perylene, phthalocyanine derivative (e.g.,copper phthalocyanine), a indanthrone, a benzimidazolone, aquinacridone, a perinone, and an azomethine derivative. In someinstances, the composition according to any method known to a personskilled in the art. For example, the colorant can be added to thethermoplastic composition in a mixing device such as an extruder,directly or else by means of a masterbatch. In various aspects, thedisclosed thermoplastic composition can comprise between about 0.005 wt% and about 5 wt % relative to the weight of the composition. In afurther aspect, the disclosed thermoplastic composition can comprisebetween about 0.01 wt % and about 3 wt % relative to the weight of thecomposition.

Textiles

As discussed herein above, a disclosed composite element can comprise atextile. The textile can be a non-woven textile, a knit textile, or awoven textile. The textile can include a plurality of fibers, aplurality of filaments, or a plurality of yarns, such that the pluralityof fibers, the plurality of filaments, or the plurality of yarnscomprise a first thermoplastic material. In some instances, theplurality of fibers, the plurality of filaments, or the plurality ofyarns can have a first and a second fiber, a first filament and a secondfilament, or a first yarn and a second yarn, such that each of the firstand the second fiber, filament, or yarn, independently have a firstthermoplastic material and an additional thermoplastic material. Forexample, a textile can have a plurality of yarns, such that the firstyarn comprises a first thermoplastic material and the second yarncomprises an additional thermoplastic material. The first thermoplasticmaterial and the additional thermoplastic material can be the same ordifferent in terms of polymer composition or a property, e.g., meltingtemperature of the polymer.

A “textile” may be defined as any material manufactured from fibers,filaments, or yarns characterized by flexibility, fineness, and a highratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments or fibers by randomly interlocking to constructnon-woven fabrics and felts. The second category includes textilesformed through a mechanical manipulation of yarn, thereby producing awoven fabric, a knitted fabric, a braided fabric, a crocheted fabric,and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer tomaterials that are in the form of discrete elongated pieces that aresignificantly longer than they are wide. The fiber can include natural,manmade or synthetic fibers. The fibers may be produced by conventionaltechniques, such as extrusion, electrospinning, interfacialpolymerization, pulling, and the like. The fibers can include carbonfibers, boron fibers, silicon carbide fibers, titania fibers, aluminafibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, andNE glasses and quartz, or the like. The fibers can be fibers formed fromsynthetic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides(e.g., an aramid polymer such as para-aramid fibers and meta-aramidfibers), aromatic polyimides, polybenzimidazoles, polyetherimides,polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol),polyamides, polyurethanes, and copolymers such as polyether-polyureacopolymers, polyester-polyurethanes, polyether block amide copolymers,or the like. The fibers can be natural fibers (e.g., silk, wool,cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can beman-made fibers from regenerated natural polymers, such as rayon,lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect its properties, such as its softness, luster, andwicking ability. The fibers can have round or essentially round crosssections. Alternatively, the fibers can have non-round cross sections,such as flat, oval, octagonal, rectangular, wedge-shaped, triangular,dog-bone, multi-lobal, multi-channel, hollow, core-shell, or othershapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21, and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COMPHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly formed of one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orrope-making techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers formed of natural, man-made and syntheticmaterials. Synthetic fibers are most commonly used to make spun yarnsfrom staple fibers, and filament yarns. Spun yarn is made by arrangingand twisting staple fibers together to make a cohesive strand. Theprocess of forming a yarn from staple fibers typically includes cardingand drawing the fibers to form sliver, drawing out and twisting thesliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn can be formed of a singlelong, substantially continuous filament, which is conventionallyreferred to as a “monofilament yarn,” or a plurality of individualfilaments grouped together. A filament yarn can also be formed of two ormore long, substantially continuous filaments which are grouped togetherby grouping the filaments together by twisting them or entangling themor both. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made of thermoplastic material). The yarn canbe made of a thermoplastic material. The yarn can be coated with a layerof a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can beexpressed using various units, including denier (D) and tex. Denier isthe mass in grams of 9000 meters of yarn. The linear mass density of asingle filament of a fiber can also be expressed using denier perfilament (DPF). Tex is the mass in grams of a 1000 meters of yarn.Decitex is another measure of linear mass, and is the mass in grams fora 10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force(expressed in units of weight, for example: pounds, grams, centinewtonsor other units) needed to break a yarn (i.e., the breaking force orbreaking point of the yarn), divided by the linear mass density of theyarn expressed, for example, in (unstrained) denier, decitex, or someother measure of weight per unit length. The breaking force of the yarnis determined by subjecting a sample of the yarn to a known amount offorce, for example, using a strain gauge load cell such as an INSTRONbrand testing system (Norwood, Mass., USA). Yarn tenacity and yarnbreaking force are distinct from burst strength or bursting strength ofa textile, which is a measure of how much pressure can be applied to thesurface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in anindustrial knitting machine, the minimum tenacity required isapproximately 1.5 grams per Denier. Most yarns formed from commoditypolymeric materials generally have tenacities in the range of about 1.5grams per Denier to about 4 grams per Denier. For example, polyesteryarns commonly used in the manufacture of knit uppers for footwear havetenacities in the range of about 2.5 to about 4 grams per Denier. Yarnsformed from commodity polymeric materials which are considered to havehigh tenacities generally have tenacities in the range of about 5 gramsper Denier to about 10 grams per Denier. For example, commerciallyavailable package dyed polyethylene terephthalate yarn from NationalSpinning (Washington, N.C., USA) has a tenacity of about 6 grams perDenier, and commercially available solution dyed polyethyleneterephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has atenacity of about 7 grams per Denier. Yarns formed from high performancepolymeric materials generally have tenacities of about 11 grams perDenier or greater. For example, yarns formed of aramid fiber typicallyhave tenacities of about 20 grams per Denier, and yarns formed ofultra-high molecular weight polyethylene (UHMWPE) having tenacitiesgreater than 30 grams per Denier are available from Dyneema (Stanley,N.C., USA) and Spectra (Honeywell-Spectra, Colonial Heights, Va., USA).

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a non-woven textile. Generally, a non-woven textileor fabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary non-woven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Non-woven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A non-woventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the non-woven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It will be further understoodthat terms, such as those defined in commonly used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the specification and relevant art and should not beinterpreted in an idealized or overly formal sense unless expresslydefined herein.

As used herein, “comprising” is to be interpreted as specifying thepresence of the stated features, integers, steps, or components asreferred to, but does not preclude the presence or addition of one ormore features, integers, steps, or components, or groups thereof.Moreover, each of the terms “by”, “comprising,” “comprises”, “comprisedof,” “including,” “includes,” “included,” “involving,” “involves,”“involved,” and “such as” are used in their open, non-limiting sense andmay be used interchangeably. Further, the term “comprising” is intendedto include examples and aspects encompassed by the terms “consistingessentially of” and “consisting of.” Similarly, the term “consistingessentially of” is intended to include examples encompassed by the term“consisting of.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items. Expressions such as “atleast one of,” when preceding a list of elements, modify the entire listof elements and do not modify the individual elements of the list.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a polymer,” “amold,” or “a foamed preform,” including, but not limited to, two or moresuch polymers, molds, or preform, and the like.

As used herein, in substance or substantially means at least 50 percent,60 percent, 75 percent, 90 percent, 95 percent, or more, as determinedbased on weight or volume.

Reference to “a” chemical compound refers one or more molecules of thechemical compound, rather than being limited to a single molecule of thechemical compound. Furthermore, the one or more molecules may or may notbe identical, so long as they fall under the category of the chemicalcompound. Thus, for example, “a” polyamide is interpreted to include oneor more polymer molecules of the polyamide, where the polymer moleculesmay or may not be identical (e.g., different molecular weights and/orisomers).

It should be noted that ratios, concentrations, amounts, and othernumerical data can be expressed herein in a range format. Where thestated range includes one or both of the limits, ranges excluding eitheror both of those included limits are also included in the disclosure,e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well asthe range greater than ‘x’ and less than ‘y’. The range can also beexpressed as an upper limit, e.g. ‘about x, y, z, or less’ and should beinterpreted to include the specific ranges of ‘about x’, ‘about y’, and‘about z’ as well as the ranges of ‘less than x’, less than y′, and‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ shouldbe interpreted to include the specific ranges of ‘about x’, ‘about y’,and ‘about z’ as well as the ranges of ‘greater than x’, greater thany′, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”,where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about‘y’”. It is to be understood that such a range format is used forconvenience and brevity, and thus, should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. To illustrate, anumerical range of “about 0.1 percent to 5 percent” should beinterpreted to include not only the explicitly recited values of about0.1 percent to about 5 percent, but also include individual values(e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and thesub-ranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent,and 4.4 percent) within the indicated range.

As used herein, the terms “about,” “approximate,” “at or about,” and“substantially” mean that the amount or value in question can be theexact value or a value that provides equivalent results or effects asrecited in the claims or taught herein. That is, it is understood thatamounts, sizes, formulations, parameters, and other quantities andcharacteristics are not and need not be exact, but may be approximateand/or larger or smaller, as desired, reflecting tolerances, conversionfactors, rounding off, measurement error and the like, and other factorsknown to those of skill in the art such that equivalent results oreffects are obtained. In some circumstances, the value that providesequivalent results or effects cannot be reasonably determined. In suchcases, it is generally understood, as used herein, that “about” and “ator about” mean the nominal value indicated plus or minus10 percentvariation unless otherwise indicated or inferred. In general, an amount,size, formulation, parameter or other quantity or characteristic is“about,” “approximate,” or “at or about” whether or not expressly statedto be such. It is understood that where “about,” “approximate,” or “ator about” is used before a quantitative value, the parameter alsoincludes the specific quantitative value itself, unless specificallystated otherwise.

As used herein, the terms “optional” or “optionally” means that thesubsequently described event or circumstance can or cannot occur, andthat the description includes instances where said event or circumstanceoccurs and instances where it does not.

As used herein, the term “units” can be used to refer to individual(co)monomer units such that, for example, styrenic repeat units refersto individual styrene (co)monomer units in the polymer. In addition, theterm “units” can be used to refer to polymeric block units such that,for example, “styrene repeating units” can also refer to polystyreneblocks; “units of polyethylene” refers to block units of polyethylene;“units of polypropylene” refers to block units of polypropylene; “unitsof polybutylene” refers to block units of polybutylene, and so on. Suchuse will be clear from the context.

The term “copolymer” refers to a polymer having two or more monomerspecies, and includes terpolymers (i.e., copolymers having three monomerspecies).

Unless otherwise specified, temperatures referred to herein are based onatmospheric pressure (i.e. one atmosphere).

Disclosed are the components to be used to prepare the compositions ofthe invention as well as the compositions themselves to be used withinthe methods disclosed herein. These and other materials are disclosedherein, and it is understood that when combinations, subsets,interactions, groups, etc. of these materials are disclosed that whilespecific reference of each various individual and collectivecombinations and permutation of these compounds cannot be explicitlydisclosed, each is specifically contemplated and described herein. Forexample, if a particular compound is disclosed and discussed and anumber of modifications that can be made to a number of moleculesincluding the compounds are discussed, specifically contemplated is eachand every combination and permutation of the compound and themodifications that are possible unless specifically indicated to thecontrary. Thus, if a class of molecules A, B, and C are disclosed aswell as a class of molecules D, E, and F and an example of a combinationmolecule, A-D is disclosed, then even if each is not individuallyrecited each is individually and collectively contemplated meaningcombinations, A-E, A-F, B-D, B-E, B—F, C-D, C-E, and C—F are considereddisclosed. Likewise, any subset or combination of these is alsodisclosed. Thus, for example, the sub-group of A-E, B-F, and C-E wouldbe considered disclosed. This concept applies to all aspects of thisapplication including, but not limited to, steps in methods of makingand using the compositions of the invention. Thus, if there are avariety of additional steps that can be performed it is understood thateach of these additional steps can be performed with any specific aspector combination of aspects of the methods of the invention.

References in the specification and concluding claims to parts by weightof a particular element or component in a composition or article,denotes the weight relationship between the element or component and anyother elements or components in the composition or article for which apart by weight is expressed. Thus, in a compound containing 2 parts byweight of component X and 5 parts by weight component Y, X and Y arepresent at a weight ratio of 2:5, and are present in such ratioregardless of whether additional components are contained in thecompound.

As used herein the terms “weight percent” indicates the percent byweight of a given component based on the total weight of thecomposition, unless otherwise specified. That is, unless otherwisespecified, all wt percent values are based on the total weight of thecomposition. It should be understood that the sum of wt percent valuesfor all components in a disclosed composition or formulation are equalto 100.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valence filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs.

The term “alkyl group” as used herein is a branched or unbranchedsaturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl,ethyl, n propyl, isopropyl, n butyl, isobutyl, t butyl, pentyl, hexyl,heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and thelike. A “lower alkyl” group is an alkyl group containing from one to sixcarbon atoms.

The term “aryl group” as used herein is any carbon-based aromatic groupincluding, but not limited to, benzene, naphthalene, etc. The term“aromatic” also includes “heteroaryl group,” which is defined as anaromatic group that has at least one heteroatom incorporated within thering of the aromatic group. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group canbe substituted or unsubstituted. The aryl group can be substituted withone or more groups including, but not limited to, alkyl, alkynyl,alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy,carboxylic acid, or alkoxy.

Unless otherwise expressly stated, it is in no way intended that anymethod set forth herein be construed as requiring that its steps beperformed in a specific order. Accordingly, where a method claim doesnot actually recite an order to be followed by its steps or it is nototherwise specifically stated in the claims or descriptions that thesteps are to be limited to a specific order, it is no way intended thatan order be inferred, in any respect. This holds for any possiblenon-express basis for interpretation, including: matters of logic withrespect to arrangement of steps or operational flow; plain meaningderived from grammatical organization or punctuation; and the number ortype of aspects described in the specification.

ASPECTS

The following listing of exemplary aspects supports and is supported bythe disclosure provided herein.

Aspect 1. A composite element comprising: a textile including aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and a second thermoplastic material surroundingthe plurality of fibers of the textile and consolidating at least aportion of the textile, wherein the second thermoplastic material has amelting temperature lower than a melting temperature of the firstthermoplastic material.

Aspect 2. The composite element of Aspect 1, wherein the textile is anon to woven textile.

Aspect 3. The composite element of Aspect 1, wherein the textilecomprises a yarn which includes the plurality of fibers, and the secondthermoplastic material surrounds at least portions of the yarn.

Aspect 4. The composite element of Aspect 3, wherein the textile is aknitted textile, a woven textile, a crocheted textile, or a braidedtextile.

Aspect 5. The composite element of any one of Aspect 1 to Aspect 4,wherein the textile is spacer textile including two textile faces, aspacer region positioned between the two textile faces, and a pluralityof spacer elements in the spacer region, the spacer elements connectingthe two textile faces, wherein the second thermoplastic materialsurrounds fibers of at least one of the two textile faces, surrounds thespacer elements, and consolidates at least one of the two textile facesand the spacer region.

Aspect 6. The composite element of Aspect 5, wherein the spacer textileis a knitted spacer textile including two knitted faces with a spaceryarn in the spacer region connecting the two knitted faces, wherein thesecond thermoplastic material at least partially surrounds yarn of atleast one of the two knitted faces, surrounds the spacer yarn, andconsolidates at least one of the two knitted faces and the spacerregion.

Aspect 7. The composite element of any one of Aspect 1 to Aspect 6,wherein the textile is essentially free of dye or pigments.

Aspect 8. The composite element of any one of Aspect 3 to Aspect 7,wherein the yarn is a package dyed yarn.

Aspect 9. The composite element of any one of Aspect 3 to Aspect 7,wherein the yarn is a solution dyed yarn.

Aspect 10. The composite element of any one of Aspect 1 to Aspect 9,wherein the first thermoplastic material comprises a thermoplasticpolymer selected from the group consisting of thermoplastic polyesters,thermoplastic polyethers, thermoplastic polyamides, thermoplasticpolyurethanes, thermoplastic polyolefins, and combinations thereof.

Aspect 11. The composite element of Aspect 10, wherein the firstthermoplastic material comprises a first thermoplastic polymer selectedfrom the group consisting of thermoplastic polyurethanes, thermoplasticpolyesters, thermoplastic polyamides, and combinations thereof.

Aspect 12. The composite element of Aspect 11, wherein the firstthermoplastic polymer is a first thermoplastic polyester.

Aspect 13. The composite element of Aspect 11, wherein the firstthermoplastic polyester is polyethylene terephthalate (PET).

Aspect 14. The composite element of Aspect 11, wherein the firstthermoplastic polymer is a first thermoplastic polyamide.

Aspect 15. The composite element of Aspect 14, wherein the firstthermoplastic polyamide is nylon 6,6, nylon 6, nylon 12, andcombinations thereof.

Aspect 16. The composite element of Aspect 11, wherein the firstthermoplastic polymer is a thermoplastic polyurethane.

Aspect 17. The composite element of Aspects 1 to 16, wherein the firstthermoplastic material comprises a first thermoplastic copolymer.

Aspect 18. The composite element of Aspect 17, wherein the firstthermoplastic copolymer is selected from the group consisting of athermoplastic co to polyester, a thermoplastic co to polyether, athermoplastic co to polyamide, a thermoplastic co to polyurethane, andcombinations thereof.

Aspect 19. The composite element of Aspect 18, wherein the firstthermoplastic copolymer is a thermoplastic co to polyester.

Aspect 20. The composite element of Aspect 18, wherein the firstthermoplastic copolymer is a thermoplastic co to polyamide.

Aspect 21. The composite element of Aspect 18, wherein the firstthermoplastic copolymer is a thermoplastic co to polyurethane.

Aspect 22. The composite element of Aspect 18, wherein the firstthermoplastic copolymer is a thermoplastic polyether block amide (PEBA)copolymer.

Aspect 23. The composite element of any one of Aspect 1 to Aspect 22,wherein the melting temperature of to the first thermoplastic materialis greater than 140 degrees Celsius (C).

Aspect 24. The composite element of any one of Aspect 1 to Aspect 23,wherein the melting temperature of the first thermoplastic material isat least 10 degrees C. greater than the melting temperature of thesecond thermoplastic material.

Aspect 25. The composite element of Aspect 24, wherein the meltingtemperature of the first thermoplastic material is at least 20 degreesC. greater than the melting temperature of the second thermoplasticmaterial.

Aspect 26. The composite element of any one of Aspect 1 to Aspect 25,wherein the second thermoplastic material comprises a secondthermoplastic polymer selected from the group consisting of athermoplastic polyester, a thermoplastic polyether, a thermoplasticpolyamide, a thermoplastic polyurethane, a thermoplastic polyolefin, andcombinations thereof.

Aspect 27. The composite element of Aspect 26, wherein the secondthermoplastic polymer is a thermoplastic polymer selected from the groupconsisting of thermoplastic polyurethanes, thermoplastic polyesters,thermoplastic polyamides, and combinations thereof.

Aspect 28. The composite element of Aspect 26, wherein the secondthermoplastic polymer is a thermoplastic polyester.

Aspect 29. The composite element of Aspect 26, wherein the secondthermoplastic polyester is polyethylene terephthalate (PET).

Aspect 30. The composite element of Aspect 26, wherein the secondthermoplastic polymer is a thermoplastic polyamide.

Aspect 31. The composite element of Aspect 30, wherein the secondthermoplastic polyamide is nylon 6,6, nylon 6, nylon 12, andcombinations thereof.

Aspect 32. The composite element of Aspect 26, wherein the secondthermoplastic polymer is a thermoplastic polyurethane.

Aspect 33. The composite element of any one of Aspect 1 to Aspect 32,wherein the second thermoplastic material comprises a secondthermoplastic copolymer.

Aspect 34. The composite element of Aspect 33, wherein the secondthermoplastic copolymer is selected from the group consisting of athermoplastic co to polyester, a thermoplastic co to polyether, athermoplastic co to polyamide, a thermoplastic co to polyurethane, andcombinations thereof.

Aspect 35. The composite element of Aspect 34, wherein the secondthermoplastic copolymer is a thermoplastic co to polyester.

Aspect 36. The composite element of Aspect 34, wherein the secondthermoplastic copolymer is a thermoplastic co to polyamide.

Aspect 37. The composite element of Aspect 34, wherein the secondthermoplastic copolymer is a thermoplastic co to polyurethane.

Aspect 38. The composite element of Aspect 34, wherein the secondthermoplastic copolymer is a thermoplastic polyether block amide (PEBA)copolymer.

Aspect 39. The composite element of any one of Aspect 1 to Aspect 38,wherein the first thermoplastic polymer of the first thermoplasticmaterial and the second thermoplastic polymer of the secondthermoplastic polymer are the same thermoplastic polymer.

Aspect 40. The composite element of Aspect 39, wherein the firstthermoplastic material and the second thermoplastic material eachcomprise a thermoplastic polyurethane.

Aspect 41. The composite element of Aspect 40, wherein a first polymericcomponent of the first thermoplastic material consists essentially of atleast one thermoplastic polyurethane, and a second polymeric componentof the second thermoplastic material consists essentially of at leastone thermoplastic polyurethane.

Aspect 42. The composite element of any one of Aspect 1 to Aspect 42,wherein the melting temperature of the second thermoplastic material isat least 10 degrees C. lower than the melting temperature of the firstthermoplastic material.

Aspect 43. The composite element of any one of Aspect 1 to Aspect 42,wherein the melting temperature of the second thermoplastic material isless than 135 degrees C.

Aspect 44. The composite element of Aspect 43, wherein the meltingtemperature of the second thermoplastic material is from about 80degrees C. to about 130 degrees C.

Aspect 45. The composite element of Aspect 43, wherein the meltingtemperature of the second thermoplastic material is from about 90degrees C. to about 120 degrees C.

Aspect 46. The composite element of Aspect 43, wherein the meltingtemperature of the second thermoplastic material is from about 100degrees C. to about 120 degrees C.

Aspect 47. The composite element of Aspect 43, wherein the meltingtemperature of the second thermoplastic material is less than 125degrees C.

Aspect 48. The composite element of Aspect 43, wherein the meltingtemperature of the second thermoplastic material is less than 120degrees C.

Aspect 49. The composite element of any one of Aspect 1 to Aspect 48,wherein the second thermoplastic material is a hot melt adhesive.

Aspect 50. A cushioning structure comprising: a first cushioningelement; and a composite element affixed to the first cushioningelement, wherein the composite element comprises a textile including aplurality of fibers, the plurality of fibers comprising a firstthermoplastic material; and a second thermoplastic material, wherein thesecond thermoplastic material has a melting temperature lower than amelting temperature of the first thermoplastic material; and wherein, inthe composite element, the second thermoplastic material surrounds theplurality of fibers in the textile and consolidates the textile.

Aspect 51. The cushioning structure of Aspect 50, wherein the firstcushioning element has an internally to facing side and an externally tofacing side opposite the internally to facing side, and the compositeelement is affixed to the internally to facing side.

Aspect 52. The cushioning structure of Aspect 50, wherein the firstcushioning element has an internally to facing side and an externally tofacing side opposite the internally to facing side, and the compositeelement is affixed to the externally to facing side.

Aspect 53. The cushioning structure of Aspect 52, wherein the externallyto facing side of the first cushioning element further comprises anouter layer affixed to a side of the composite element opposite the sideaffixed to the externally to facing side of the cushioning element.

Aspect 54. The cushioning structure of Aspect 53, wherein the cushioningstructure is a cushioning structure for an article of footwear, theinternally to facing side is an upper to facing side, the externally tofacing side is a ground to facing side, and the outer layer is anoutsole layer.

Aspect 55. The cushioning structure of any one of Aspect 50 to Aspect54, wherein the cushioning structure further comprises a secondcushioning element, and the composite element is positioned between andaffixed to both the first cushioning element and the second cushioningelement.

Aspect 56. The cushioning structure of Aspect 55, wherein the firstcushioning element is a foam component or a fluid chamber, and thesecond cushioning element is a foam component or a fluid chamber.

Aspect 57. The cushioning structure of Aspect 56, wherein the firstcushioning element is a foam component, and the second cushioningelement is a fluid chamber.

Aspect 58. The cushioning structure of Aspect 56, wherein the firstcushioning element is a fluid chamber, and the second cushioning elementis a foam component.

Aspect 59. The cushioning structure of any one of Aspect 50 to Aspect57, wherein the first cushioning element is a fluid chamber having afirst side, a second side, and a sidewall extending between the firstside, wherein the composite element extends across and is affixed to atleast a portion of the first side of the fluid chamber, to the secondside of the fluid chamber, to the sidewall of the fluid chamber, or toany combination thereof.

Aspect 60. The cushioning structure of Aspect 56, wherein the first sideof the fluid chamber and at least a portion of the sidewall are formedof a first sheet comprising a third thermoplastic material, the secondside of the fluid chamber is formed of a second sheet comprising afourth thermoplastic material.

Aspect 61. The cushioning structure of any one of Aspect 50 to Aspect60, wherein the composite element is a composite element according toany one of 1 to 49.

Aspect 62. The cushioning structure of any one of Aspect 50 to Aspect61, wherein the cushioning structure is a fluid chamber according to anyone of 50 to 164.

Aspect 63. The cushioning structure of any one of Aspect 50 to Aspect61, wherein the cushioning structure is a cushioning structure for anarticle of apparel.

Aspect 64. The cushioning structure of any one of Aspect 50 to Aspect61, wherein the cushioning structure is a cushioning structure for anarticle of sporting equipment.

Aspect 65. The cushioning structure of any one of Aspect 50 to Aspect61, wherein the cushioning structure is a sole structure for an articleof footwear.

Aspect 66. The cushioning structure of any one of Aspect 61 to Aspect65, further comprising an outsole having a chamber to engaging side anda ground to engaging side, wherein the chamber to engaging side of theoutsole covers and is affixed to at least a portion of the ground tofacing side of the fluid chamber.

Aspect 67. The cushioning structure of Aspect 66, wherein the chamber toengaging side of the outsole is affixed to at least a portion of thesidewall of the fluid chamber.

Aspect 68. The cushioning structure of any one of Aspect 61 to Aspect67, further comprising a mid to sole having a ground to facing sideaffixed to the second side of the fluid chamber.

Aspect 69. The cushioning structure of any one of Aspect 61 to Aspect68, wherein the outsole comprises a second composite element between thechamber to engaging side of the outsole and a portion of the ground tofacing side of the fluid to filled chamber.

Aspect 70. The cushioning structure of any one of Aspect 61 to Aspect69, wherein the outsole comprises a second composite element between thechamber to engaging side of the outsole and a portion of the ground tofacing side of the fluid to filled chamber.

Aspect 71. The cushioning structure of Aspect 70, wherein the secondcomposite element is a composite element according to any one of Aspect1 to Aspect 49.

Aspect 72. An article of footwear, comprising: an upper; and a solestructure affixed to the upper, wherein the sole structure includes acushioning structure according to any one of Aspect 50 to Aspect 71.

Aspect 73. An outsole for an article of footwear, the outsolecomprising: a composite element according to any one of 1 to 49.

Aspect 74. A method of manufacturing a composite element, the methodcomprising: positioning a textile and film adjacent to each other,wherein the textile includes a plurality of fibers, the plurality offibers comprising a first thermoplastic material; and wherein the filmcomprises a second thermoplastic material has a melting temperaturelower than a melting temperature of the first thermoplastic material;and increasing a temperature of the film to a temperature at or abovethe melting temperature of the second thermoplastic material but belowthe melting temperature of the first thermoplastic material, such thatthe second thermoplastic flows and surrounds the plurality of fibers ofthe textile and consolidates the textile; and decreasing the temperatureof the film to a temperature below the melting temperature of the secondthermoplastic material such that the second thermoplastic re tosolidifies, forming the composite element.

Aspect 75. The method of Aspect 74, wherein the method further comprisesapplying pressure to the textile and film while the temperature of thefilm is above the melting temperature of the second thermoplasticmaterial.

Aspect 76. The method of Aspect 74 or Aspect 75, wherein the step ofincreasing the temperature is conducted while the textile and the filmare in a mold, and the method further comprises removing the compositeelement from the mold.

Aspect 77. The method of any one of Aspect 74 to Aspect 76, wherein thecomposite element is a composite element according to any one of Aspects1 to 49.

Aspect 78. A method of making a cushioning structure, the methodcomprising: affixing a composite element to a first cushioning element;wherein the composite element comprises a textile including a pluralityof fibers, the plurality of fibers comprising a first thermoplasticmaterial; a second thermoplastic material, wherein the secondthermoplastic material has a melting temperature lower than a meltingtemperature of the first thermoplastic material; and, in the compositeelement, the second thermoplastic material surrounds the plurality offibers in the textile and consolidates the textile.

Aspect 79. The method of Aspect 78, wherein the cushioning structure hasan internally to facing side and an externally to facing side oppositethe internally to facing side, and the affixing comprises affixing thecomposite element to the internally to facing side.

Aspect 80. The method of Aspect 78, wherein the cushioning structure hasan internally to facing side and an externally to facing side oppositethe internally to facing side, and the affixing comprises affixing thecomposite element to the externally to facing side.

Aspect 81. The method of any one of Aspect 78 to Aspect 80, wherein themethod further comprises affixing an outer layer to a side of thecomposite element opposite the side affixed to the externally to facingside of the cushioning element.

Aspect 82. The method of any one of Aspect 78 to Aspect 81, wherein themethod further comprises affixing a second cushioning element to thefirst cushioning element or the composite element.

Aspect 83. The method of Aspect 82, wherein the method further comprisespositioning the composite element between the first cushioning elementand the second cushioning element, and affixing the composite element toboth the first cushioning element and the second cushioning element.

Aspect 84. The method of any one of Aspect 78 to Aspect 83, wherein thecushioning structure is a cushioning structure according to any one ofAspect 50 to Aspect 71.

Aspect 85. A method of manufacturing an article, comprising: affixing afirst component to a cushioning structure, wherein the cushioningstructure is a cushioning structure according to any one of Aspect 50 toAspect 71.

Aspect 86. The method of Aspect 85, wherein the first component is anupper for an article of footwear, and the cushioning structure is a solestructure for an article of footwear.

Aspect 87. The method of Aspect 85 or Aspect 86, wherein the step ofaffixing comprises affixing the first component to the cushioningstructure using an adhesive.

Aspect 88. The method of Aspect 85 or Aspect 86, wherein the step ofaffixing comprises affixing the first component to the cushioningstructure comprises forming a heat bond between the first component andthe cushioning structure by melting a portion of the secondthermoplastic material of the composite element.

From the foregoing, it will be seen that aspects herein are well adaptedto attain all the ends and objects hereinabove set forth together withother advantages which are obvious and which are inherent to thestructure.

While specific elements and steps are discussed in connection to oneanother, it is understood that any element and/or steps provided hereinis contemplated as being combinable with any other elements and/or stepsregardless of explicit provision of the same while still being withinthe scope provided herein.

It will be understood that certain features and sub-combinations are ofutility and may be employed without reference to other features andsub-combinations. This is contemplated by and is within the scope of theclaims.

Since many possible aspects may be made without departing from the scopethereof, it is to be understood that all matter herein set forth orshown in the accompanying drawings and detailed description is to beinterpreted as illustrative and not in a limiting sense.

It is also to be understood that the terminology used herein is for thepurpose of describing particular aspects only, and is not intended to belimiting. The skilled artisan will recognize many variants andadaptations of the aspects described herein. These variants andadaptations are intended to be included in the teachings of thisdisclosure and to be encompassed by the claims herein.

Now having described the aspects of the present disclosure, in general,the following Examples describe some additional aspects of the presentdisclosure. While aspects of the present disclosure are described inconnection with the following examples and the corresponding text andfigures, there is no intent to limit aspects of the present disclosureto this description. On the contrary, the intent is to cover allalternatives, modifications, and equivalents included within the spiritand scope of the present disclosure.

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations, and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

What is claimed:
 1. A cushioning structure comprising: a firstcushioning element; and wherein the first cushioning element is a fluidchamber; a composite element affixed to the first cushioning element,wherein the composite element comprises a textile including a pluralityof fibers, the plurality of fibers comprising a first thermoplasticmaterial; and a second thermoplastic material, wherein the secondthermoplastic material has a melting temperature lower than a meltingtemperature of the first thermoplastic material; wherein, in thecomposite element, the second thermoplastic material surrounds theplurality of fibers in the textile and consolidates the textile.
 2. Thecushioning element of claim 1, wherein the first cushioning element hasan internally-facing side and an externally-facing side opposite theinternally-facing side, and the composite element is affixed to theinternally-facing side.
 3. The cushioning element of claim 1, whereinthe first cushioning element has an internally-facing side and anexternally-facing side opposite the internally-facing side, and thecomposite element is affixed to the externally-facing side.
 4. Thecushioning structure of claim 3, wherein the externally-facing side ofthe first cushioning element further comprises an outer layer affixed toa side of the composite element opposite the side affixed to theexternally-facing side of the cushioning element.
 5. The cushioningstructure of claim 1, wherein the cushioning structure further comprisesa second cushioning element, and the composite element is positionedbetween and affixed to both the first cushioning element and the secondcushioning element.
 6. The cushioning structure of claim 1, wherein eachof the first cushioning element and the second cushioning element is afoam component.
 7. The cushioning structure of claim 1, wherein thetextile is a knitted textile, a woven textile, a crocheted textile, or abraided textile.
 8. The cushioning structure of claim 1, wherein thetextile is a non-woven textile.
 9. The cushioning structure of claim 1,wherein the textile comprises a fiber, a filament, or a yarn, and thesecond thermoplastic material surrounds at least portions of the fiber,the filament, or the yarn.
 10. The cushioning structure of claim 1,wherein the textile is spacer textile including two textile faces, aspacer region positioned between the two textile faces, and a pluralityof spacer elements in the spacer region, the spacer elements connectingthe two textile faces, wherein the second thermoplastic materialsurrounds fibers of at least one of the two textile faces, surrounds thespacer elements, and consolidates at least one of the two textile facesand the spacer region.
 11. The cushioning structure of claim 1, whereinthe first thermoplastic material comprises a first thermoplastic polymerselected from the group consisting of thermoplastic polyurethanes,thermoplastic polyesters, thermoplastic polyamides, and combinationsthereof.
 12. The cushioning structure of claim 1, wherein the meltingtemperature of the second thermoplastic material is at least 10 degreesC. lower than the melting temperature of the first thermoplasticmaterial.
 13. The cushioning structure of claim 1, wherein thecushioning structure is a midsole for an article of footwear.
 14. Amethod of making a cushioning structure, the method comprising: affixinga composite element to a first cushioning element; wherein the compositeelement comprises a textile including a plurality of fibers, theplurality of fibers comprising a first thermoplastic material; a secondthermoplastic material, wherein the second thermoplastic material has amelting temperature lower than a melting temperature of the firstthermoplastic material; and, in the composite element, the secondthermoplastic material surrounds the plurality of fibers in the textileand consolidates the textile.
 15. The method of claim 14, wherein thecushioning structure has an internally-facing side and anexternally-facing side opposite the internally-facing side, and theaffixing comprises affixing the composite element to theinternally-facing side.
 16. The method of claim 143, wherein thecushioning structure has an internally-facing side and anexternally-facing side opposite the internally-facing side, and theaffixing comprises affixing the composite element to theexternally-facing side.
 17. The method of claim 14, wherein the methodfurther comprises affixing an outer layer to a side of the compositeelement opposite the side affixed to the externally-facing side of thecushioning element.
 18. The method of claim 14, wherein the methodfurther comprises affixing a second cushioning element to the firstcushioning element or the composite element.
 19. The method of claim 14,wherein the method further comprises positioning the composite elementbetween the first cushioning element and the second cushioning element,and affixing the composite element to both the first cushioning elementand the second cushioning element.
 20. The method of claim 14, whereinthe cushioning structure is a midsole for an article of footwear.